Process of making carbon chlorids, &amp;c.



- Carbon Halids; and I do hereby declare UNITED STATES. PATENT". oFFroE.

HENRY S. BLAGKMORE, OF

MOUNT VERNON, NEW YORK.

rnocnss OF MAKING CARBON GHLORIDS, am. I

To all whom it my. concern: I w

Be it known that I, HENRY S. BLAOKMORE, a citizen of the United States, residing at -Mount Vernon, in the county of Westchester and State of New York, have invented certain new and useful Improvements in Processes of Making Carbon Chlorids and other the following to'be-a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appert'ains to make and use the same.

The object of my invention is to make carbon chlorids, such as carbon tetrachlorid and thermic carbid such as acetylene (hydrogen carbid), calcium carbid, or other metallic carbid, the electro-positive element or base of which is removed by the excess of chlorin,

1 oxygen or other, combining element resent,

' temperature of the reacting ingredients being,

and chlorin which is generated in ,t e presence of said endothermiccarbid or carbon which, heated to a combining degree, either externally or by. the heat'ofreaction', l the maintained below the dissociating point of the carbon chlorid desired preferably by refrigeration but is not confined to this operation as the heat required may; be wholly supplied externally to produce the reaction and the temperature regulated and maintained below the dissociating point of the carbon chlorid-by any convenient means.

In carrying out my invention for the production of carbon chlorid I prefer to proceed as follows; 'I take a mixture of calcium hypochlorite Ca(ClO) "(bleaching powder) and calcium carbid CaC in a powdered and thoroughly' mixed condition and in'proportion of about 36 pounds of the former to .6 pounds of the latter and ,placeitin a pro er recep- I -acommunicating with a con enser.

Specification of Letters Patent. Application filed January 12, 1903. Serial No. 138,737.

Patented. June ,2, 190 8;

then'convey into the receptacle hydrochloric acid gas whereupon a reaction occurs generating carbon tetrachlorid whichis vaporized by the heat liberated during reaction, distilled off and is finally condensed in any convenient manner. This reaction which takes place may be illustrated by the following chemical formula or equation: 1

Care must be taken not to introduce the hydrochloric acid gas into contact with the mixture of calcium hypochlorite and c'alcium carbid too rapidly, otherwise the heat will accumulate suddenlyto a point at which the formation of carbon tetrachlorid is precluded and also the danger of explosion from the too rapid generation of carbon chlorid vapors or an excess of acetylene is avoided. I find it of advantage to introduce together with the hydrochloric acid gas a gas of inert nature such as nitrogen which can be cooled prior to introduction-or can be employed in such heat liberated during reaction thereby acting as a refrigerant to maintain the temperature below the dissociating point of the carbon chlorids desired.

volume that it will absorb the excess The essential feature of my process is the formationof carbon chlorids by subjecting carbon ,or carbon-yielding compounds to the action of nascent chlorin or exposing the carbon or=carbon-yielding substance-to the action of. a chlorin-yieldmgbompound or composition at a reacting temperature.

Instead of mixing, with the calc um h ochlorite-a solid carbid such as'calcium car id I can convey in contact'with the hypochlorite a mixture of a gaseous or vaporized hydrocarbon with gaseous hydrochloric acid whereupon the liberation of chlorin and car bon is eflected simultaneously by the oxidation of the hydrogen content oflthe hydrochloric acid and hydrocarbon with simultaneous deoxidation of the hypo chlorite, the chlorin and carbon thus liberated unitin in their nascent condition to form carbon 0 lorids; the chemical reaction whichtakes lace under these conditions during the per ormance of my process may be illustrated by the following chemical formula or: equation which setsforth the formation of carbon chlorids by the oxidation of the hydrogen content of hydrochloric acid and acetylene:

It is obvious that the temperature'of the reacting ingredients must be maintained at a point at which the oxygen has an afiinity for the hydrogen of the composition in prefer ence to carbon which is found to be preferably at a low red heat and any other oxidizing agent instead of calcium hypochlorite may be employed to oxidize the hydrogen content of the composition or free oxygen may be employed provided, as aforesaid, the

temperature is maintained at a point at which the hydrogen has an affinity for the oxygen in preference to carbon.

ploying free oxygen the reaction simply illustrated by formula or equation:

I do not desire. to confine myself to the production of carbon chlorids by exposing carbon or carbon-yielding substances to the action of nascent chlorin generated in the preferable manner as hereinbefore described, viz. the formation of chlorin by the action of hydrochloric acidon calcium h ochlorite, but reserve the right to produce the may be the following chemical chlorin in any convenient manner so 10 as I employ as carbon-yielding substances car-- bids of endothermic nature,

out danger of dissociation.

it is generated in the presence of the car on or carbon-yielding substance with which the nascent chlorin may readily combine with- .While I consider it of great advantage to such as acetylene, calcium carbid, or other metallicrcar-v bids so that the process may be carried on .continuously by the heat liberated during reaction, still, I can employ such carbon or carbon-yielding substances as are capable of uniting with nascent chlorin to produce carbon chlorids which require the employment of extraneous heat toperform and maintain the reaction whichcan either be supplied by sociation, in the former case, such as the liberation of carbon from acetylene or calcium carbid by the combination of chlorin, oxygen or other combining agent with the hydrogen of the acetylene, calcium of the When em-' under which app calcium carbid or other base of the carbid employed, or, in the latter case, the'physical dissociation of acetylene by the action of heat into free carbon such as is knownby the term k g I also do not desire to confine myself to the performance of the direct reaction between nascent chlorin and free carbon but desire to include all modifications which may justly come within the scope of my invention such as the performance of the reaction in a fused condition or dissolved or suspended in inert fluid which inert substances may be designated as those which do not interfere with the formation or separation of the carbon chlorids desired; or simultaneously generating chlorin and carbon or carbon-yielding substances in the presence of a reacting fluid; or introducing into contact with a.

chlorin-generating composition carbon or carbon-yielding substances contmuously or from time to tlme as desired; or exposing the carbon or carbon-yielding substance to t the action of nascent chlorin in any practical manner so long as the temperature is soregulated and maintained by refrigeration or..other'wise'a't a point at which the electropositive element or base of the carbon-yielding compound has an aflinity for the negative decomposing agent employed in preference to carbon and is below the dissociating point of the carbon chlorid desired.

The term carbid employed inthis specification and claims relates to any combination of. carbon with an element, such as a metal or-metals, be it a normal carbid, an

acetylid or any-union or combination which may; be; considered the equivalent of the same, and is intended to include hydrogen carbids (hydrocarbons) as well as calcium carbid or other metal carbids hydrogen being taken as a metal which exists in gaseous form at ordinary temperature and pressure, ,the

carbid of which may be justly termed, and is herein intended to include the hydrogen carbids (hydrocarbons), as well as metal or other carbids. The hydrogen carbids employed may be either in solid, liquid, or gaseous form.

-As an illustration of-- the hydrocarbons which can be em loyed and the conditions permanent gas, acetylene, or, in vaporized condition,

dense hydrocarbon.

As a compound or composition from which chlorin is evolved or generated in the presence of carbon or carbon-yielding substances Ihprefer to employ hydrogen'chlorid (hydroc oric. acid gas) the chlorin from which is tent but I do not confine myself to the emchlorid or chlorin compound may be emed Ifwould mention as a.

naphthalene, petroleum, etc.-, or, V in sohd form, bituminous coal or similar liberated by oxidation of the hydrogen conployed "from which the chlorin may be evolved incontact with the carbon or carhon-yielding compound by any convenient means, such as the decomposition of calcium chlorid and calcium hy ochlorite by the action of'silica and heat, t us:

The term oxidizing agent which is em-.

ployed herein refers to an compound which Wlll combine with the e ectro-positive ele- .ment or elements of the-chlorin com'posi tion, the telectro-positive constituents of the carbOnaceous substance, or both, and may -be either'a compound from which the oxygen may be derived during reaction or oxygen rmxed wlth other substances such as ordlnary air or oxygen per se. The terms car- --bon chlorid and carbon'halid employed in this specification and claims relate to any combination of carbon with chlorin or other halogen be it the tetrachlorid, tetrahalid, or

' any other suitable chlorin or halogen com- ,cured, after formation, inany convenient manner. I have also found it advantageous to subject the halogen generated to the ac- -tion of an. electric current whereby the said halogen becomes energized or rendered more 1 active and its union with the carbon faciliof an electric current I desireto include as an .tated and the. employment of halogen thus energized and rendered active by the action im ortant feature of my invention.

t is obvious that-I can produce, any other carbon halid, such as carbon tetrabromid,

carbon tetrafiuorid, or carbon tetraiodid by exposing carbon -or carbon-yielding substances, to the action of-a halogen composltion without departing from the invention;

Instead of simultaneously liberating in contact with each other the carbon from carbon-containing compounds and chlorin from compositions containingvchlorin, I can employ the carbon in a free state and generate the chlorin in contact with it Without departing from the spirit of my invention which consists in generating chlorin or other halogen in the presence of carbon or carbon- .yielding substances under conditions which admit of their union to form carbon halids.

spirit of my When carryin out this modification of my process I emp o a mass of porous carbon, such as charcoa ,preferably in a pulverized condition and pass a current-of electricity through the same. I then supply to the carthrough, molten calcium chlorid. As this calcium chlorid passes through the pulveru- ,lent and porous charcoal it is disrupted by the action of the electric current producing calcium carbid and carbon tetrachlorid. The reaction which takes placemaybe illustrated by the following chemical formula or equation: a

ZCaCl 50 ZCaC 1+ 001 This process can be carried-on continuously by supplying calcium chlorid and pulverized charcoal from time to time while' maintaining the passage of an electric current through the mass and withdrawing the calcium cari hon during the passage of electricity therebid produced, the carbon tetrachlorid which i is produced by the action of nascent chlorin thus generated on the powdered or porous charcoal passing off as vapor and being condensed and collected in any convenient manner. stituted for the calcium chlorid in which case the corresponding carbon halids will be evolved instead of carbon tetrachlorid.

The reactions which take place between the ingredients in carrying out my process as hereinbefore set forth are induced and maintained either by heat applied from an external source or liberated within the mass by the decomposition or transformation of endothermic compounds or by electrical re- Any other metallic halid may be subsistance, the excess of heat being abstracted from the ingredients tomaintain the temperature below the dissociating point of the carbon halid desired by refrigeration or other convenient means. I

Having now describ i my invention, what I claim as new and desire to secure by Letters Patent is which consists in exposing a carbonaceous substance to the action of halogen-generating composition under reacting conditions.

-2.. The process of making carbon halids which consists in exposing a carbid to the action of a halogen generating composition under reacting conditions.

V 3. The process of making carbon halids which consists in exposing a metallic carbid to the action of a halogen-generating composition under'reacting conditions.-

4. The process of making carbon halids which consists in exposing hydrogen carbid to the action of a halogen-generating com-. position under reacting conditions.

5. The process of making carbon hallds which consists in exposing acetylene to the 'action of halogen generating composition under reacting conditions and maintaining the temperature below the dissociating point of the carbon halid desired.

' induced between the'i'ngredients of the substance, maintaining the tem erature of the reacting" ingredieiits below t edissociating point of the carbon halid desired and colecting and condensing the vapors evolvedv during reaction.

8. The process of making carbon chlorid which consists in exposing a carbonaceous substance to the action of a chlorin generat ing composition. 0

9.. The process of making carbon chlorid which consists in exposing a carbonaceous substance to the action of nascent chlorin.

10. The process of making carbon chlorid which consists in exposing a carbonaceous substance to the action of nascent chlorin while maintaining the temperature below the dissociating point of the carbon chlorid desired.

11. The process of making carbon chlorid which consists in exposing a carbonaceous substance to the action of nascent chlorin while maintaining the temperature below the dissociating point of the carbon chlorid desired by refrigeration.

.12. The process of making carbon chlorid which consists in di lacing chlorin from a composition containing chlorin in the presence of a carbonaceous substance which carbonaceous substance is ca able of uniting or combining with the chlorin thus displaced.

13. The process of making carbon chlorid which consists in exposing acarbonaceous substance and a chlorid to the action of an oxidizing agent at a temperature at which the oxygen of the oxidizing agent has an aflinity for the electro-positive element of the chlorid inpreference to carbon.-

. 14. The process of making carbon chlorid which consists in exposin substance andhydrogen'chlorid to the action of an oxidizing agent at a temperature at I which the oxygenof the oxidizing agent has an aflinity for-hydrogen in preference t6 carbon. I I

15. The process of making carbon chlorid which consists in exposing a carbonaceous substance and hydrogen chlorid to the action of oxygen while maintainingthe temperature ata point at which oxygen has an aflinity for a carbonaceous the electropositive constituents of the coma position in preference to carbon.

16. The process of making carbon chlorid which consists in exposing acarbidto the action of a chlorin-generating composition. 1.7. The process of making carbon chlorid which consists in exposing a carbid and a chlorid to the action of an oxidizing agentat 'a temperature at wvhich the oxygen of the oxidiz ng agent has'an aflinity for the elec-:

preference to carbon.

- 18. The process of making carbon chlorid which consists .in exposing a carbid and a tro-positive element of the composition in compound containing chlorin to the action' of a substance capable of simultaneously dis placing carbon and chlorin whereby they unite concurrently by mutual contact. v 19. The process of making carbon chlorid which consists in exposing a carbid and hy-' drogen chlorid to the action'of an oxid zing agent at a temperature at which the oxygen of the oxidizing agent has an affinity for .the

electro-positive element ofthe composition in preference to carbon.

20. The process of making carbon chlorid which consists in exposing a carbid and hydrogen chlorid to the action of oxygen at a temperature at which the oxygen has an affinity for the electro-positive constituents of the composition in preference. to carbon. .21. The process of making carbon chlorid which consists in exposing a metal carbid to the action of a chlorin-generating coinposi- I v tion. 3

22. The process ofi making, carbon chlorid which consists in exposing a metal'carbid and a chlorid to the action of an oxidizing agent at ateinperature at which the oxygen of the oxidizing agent has an affinity for the electro-positive element of-.the composition in preference to carbon.

23. The process of making carbon chlorid which cons sts in exposing a metal carbid and hydrogen chlorid to the action of an oxidizing agent at a temperature at which the oxygen of the oxidizing agent has an affinity for the electro-fpositive element of the composition in pre erence to carbon.

24. The process of making carbon chlorid which consists in exposing a metal carbid and hydrogen chlorid to the action of oxygen while maintaining thetemperature at a point at which the oxygen'has an aifinity for the eleetro-positive constituent in preference to carbon. 7

25.. The process of making carbon chlorid 1 which consists in exposing. acetylene to the action of a chlorin generating composition.-

26. The process of making carbon chlorid 'which consists in exposing a com o'sition containing a metal carbid and a 0 012111 to the'action of a substance capable of uniting with the electro-positive constituents of the composition, wliereby the displaced carbon in preference to carbon.

and chlorid concurrently unite by mutual contact.

27 The process of making'carbon chlorid which consists in exposing hydrogen carbid and a chlorid to the action of an oxidizing agent at a temperature at which the oxygen of the oxidizing agent has an aflinity for the electro-positive element of the composition in preference to carbon.

28. The process of making carbon chlorid which consists in exposing hydrogen carbid and hydrogen chlorid to the action of an oxidizing agent at a temperature at which the oxygen of the oxidizing agent has an aflinity for hydrogen in preference to carbon.

29. The process of making carbon chlorid which consists in exposing a hydrogen carbicl and hydrogen chlorid to, the action of oxygen while maintaining the temperature at a point at which oxygen has an affinity for the electro-positive constituents of .the composition 30. The process of makin carbon chlorid which consists in exposing a ydrogen carbidand a chlorid to the action of a substance capable of uniting with the electro-positive constituents of the com osition whereby the displaced carbon and c orin concurrently unite y mutual contact. 7

31: The process of making carbon chlorid which consists in exposing acetylene and a chlorid to the action ofa substance capable of uniting with the electro-positive constituents of the com ositionwhereby the dis.

placed carbon an chlorin concurrently unite y mutual contact.

32. The process of I which consists in exposing acetylene and a 1 chlorid tothe action of an oxidizing agent at a temperature at which the oxfygen of the agenthas an aflinity or the electroositiye-elements of the composition p erence .to. carbon.

- 33. The process of making carbon chlorid which conslsts in exposing acet lene and hydrogen chlorid to the actiono agent at a temperatureat which the oxygen of the oxidizing agent has an aflinity for ydrogen in preference to carbon. I a

'34. The process of making carbon chlorid which consists in exposing acetylene'and hydrogen chlorid to the actipn of oxygen while maintaining the temperature at a point at which the oxygen has an aflinity for the hydrogen of the composition in preference to carbon.

35. The process of making carbon chlorid .which consists in exposing an endothermic carbid and a chlorid to the action of a chlorin generating composition. a

"36. The rocess of making carbon chlorid which consists in exposing anendothermic carbid and a chlorid to the action of an oxidizing agent at. a' temperature at which the oxygen of thetoxidizing agent has an affinity for the electro-positive element of the'composition in preference to carbon.

an oxidizing 37 The process of making carbon chlorid which consists in exposing an'endothermic carbid and hydrogen chlorid to the action of oxygen while maintaining the temperature at a oint at which the oxygen has an afiinity for t e electro-positive constituents of the composition in preference to carbon.

38. The process of making carbon chlorid which consists in exposing an endothermic carbid and a chlorid to the action of a substance capable of simultaneously displacing j the carbon and chlorin whereby they unite making carbon chlorid 

